JP6467660B2 - Polyol composition and polyurethane foam - Google Patents

Description

  The present invention relates to a polyol composition and a polyurethane foam, and particularly relates to a polyol composition and a polyurethane foam obtained using the polyol composition.

  Conventionally, polyurethane foam is produced by reacting and foaming a polyol and a polyisocyanate in the presence of a foaming agent.

  As the polyol, generally known are polyether polyols obtained by addition polymerization of polyalkylene oxides using polyhydric alcohol as an initiator, and polyester polyols obtained by condensation polymerization of polyhydric alcohols and polybasic acids. It has been.

  Such polyether polyols and polyester polyols are petrochemical products derived from petroleum. However, in recent years, there is a concern about the depletion of petroleum, and petrochemical products emit a large amount of carbon dioxide when incinerated. There are concerns about the impact on the global environment.

  Therefore, as a polyol, a polyol using biomass as a raw material has been proposed instead of a polyol using petrochemical products as a raw material. Biomass emits carbon dioxide when it is burned, while the organism that is its starting material, especially plants, absorbs carbon dioxide in the atmosphere through photosynthesis during growth. Corresponds to carbon neutral, which does not substantially increase carbon dioxide.

  As such a polyol using biomass as a raw material, for example, a polyester polyol using castor oil as a raw material has been proposed.

  It is also known that the biomass-derived polyester polyol is used as a raw material for polyurethane foam by mixing with petroleum-derived polyether polyol.

  On the other hand, when a biomass-derived polyester polyol and a petroleum-derived polyether polyol are mixed, phase separation may be caused, and when the phase-separated polyol mixture is used for the production of polyurethane foam, the resulting foam machine Physical properties (hardness, tensile strength, elongation, tear strength, etc.) may decrease.

  Therefore, it has been proposed to add a compatibilizer in the mixing of the biomass-derived polyester polyol and the petroleum-derived polyether polyol.

  More specifically, for example, in a polyol composition containing a polyester polyol, a polyether polyol and a compatibilizing agent, it has been proposed to use trimethylolpropane and its alkylene oxide adduct as a compatibilizing agent ( Patent Document 1).

  Further, for example, in a polyol composition containing a polyester polyol, a polyether polyol and a compatibilizer, the compatibilizer has a hydroxyl value of 20 to 120 mg KOH / g, and HLB is HLB of the polyester polyol and HLB of the polyether polyol. Among them, a compatibilizer lower by 0.3 or more than the lower HLB value is used, and the blending amount is 0.1 to 10% by mass per 100% by mass of the polyol composition. (See Patent Document 2).

  Moreover, in order to suppress phase separation in mixing of vegetable oil-based polyols such as soybean oil-based polyols and non-vegetable oil-based polyols such as propylene oxide / ethylene oxide polyether polyols, aliphatic alcohol ethoxylates and / or aliphatic phenol ethoxys are used. It has been proposed to mix the rates (see Patent Document 3).

JP 2010-207622 A JP 2010-202761 A JP 2007-277560 A

  However, while the above polyol composition can suppress phase separation between the polyester polyol and the polyether polyol, the polyurethane foam obtained using the polyol composition has mechanical properties such as durability (for example, Wet heat compression set) may not be sufficient.

  In addition, since the polyol composition may be stored outdoors in the summer or may be transported, it can be used for a long time not only at room temperature but also in a relatively high temperature environment (for example, 50 ° C. or more). It may be required to suppress separation.

  An object of the present invention is to provide a polyol composition capable of suppressing phase separation over a long period of time at room temperature and a relatively high temperature environment, and capable of obtaining a polyurethane foam having excellent mechanical properties, and the polyol composition It is providing the polyurethane foam obtained by using.

  The polyol composition of the present invention is a polyol composition containing a polyol component and a phase separation inhibitor, which contains the following component (A) and the following component (B) as the polyol component, and the following as the phase separation inhibitor: It contains the component (C).

Component (A): Polyester polyol which is a condensate of a plant-derived fatty acid which may be condensed and a polyhydric alcohol Component (B): Polyether polyol Component (C): Polyoxyethylene addition of a hydroxyl group-containing fatty acid ester Further, in the polyol composition of the present invention, it is preferable that the plant-derived fatty acid contains a hydroxyl group-containing fatty acid.

  In the polyol composition of the present invention, it is preferable that the plant-derived fatty acid contains a castor oil fatty acid.

  In the polyol composition of the present invention, it is preferable that the hydroxyl group-containing fatty acid contains a hydroxyl group-containing monocarboxylic acid.

  In the polyol composition of the present invention, it is preferable that the hydroxyl group-containing fatty acid contains ricinoleic acid.

  In the polyol composition of the present invention, the component (C) contains a polyoxyethylene adduct of hardened castor oil, and in the polyoxyethylene adduct of the hardened castor oil, the average added mole number of ethylene oxide is the hardened castor oil. It is suitable that it is 45 mol or more and 120 mol or less with respect to 1 mol.

Further, in the polyol composition of the present invention, the polyoxyethylene adduct (component (C _S )) of the component (A), the component (B), and a hydroxyl group-containing fatty acid ester having an average addition mole number of ethylene oxide of p _S. If, polyoxyethylene adducts of hydroxyl-containing fatty acid esters average addition mole number of ethylene oxide is p _L becomes at least in blending the (component (C _L)), it is preferable that a p S _{<p L} .

  In the polyol composition of the present invention, it is preferable that the hydroxyl value of the component (B) is 15 mgKOH / g or more and 80 mgKOH / g or less.

  Moreover, in the polyol composition of this invention, it is suitable that the hydroxyl value of a component (A) is 30 mgKOH / g or more and 120 mgKOH / g or less.

  In the polyol composition of the present invention, the content ratio of the component (A) is 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total amount of the polyol component and the phase separation inhibitor. Is preferred.

  Moreover, in the polyol composition of this invention, the content rate of a component (C) is 0.5 mass part or more and 10 mass parts or less with respect to 100 mass parts of total amounts of the said polyol component and the said phase-separation inhibitor. Is preferred.

  The polyurethane foam of the present invention is characterized by being obtained by reacting the above polyol composition with a polyisocyanate component.

  The polyol composition of the present invention contains a polyoxyethylene adduct of a hydroxyl group-containing fatty acid ester as a phase separation inhibitor. Therefore, even if a polyester polyol and a polyether polyol are mixed, the polyol composition is used at room temperature and in a relatively high temperature environment. , Phase separation can be suppressed over a long period of time.

  Moreover, if the polyol composition of the present invention is used, a polyurethane foam having excellent physical properties can be obtained.

  In addition, since the polyurethane foam of the present invention is obtained using the polyol composition of the present invention, it has excellent mechanical properties (such as durability).

  The polyol composition of the present invention contains a polyol component and a phase separation inhibitor, and contains a polyester polyol (component (A)) and a polyether polyol (component (B)) as the polyol component. .

  Component (A) is a condensate of an optionally derived plant-derived fatty acid and a polyhydric alcohol (hereinafter, component (A) is also referred to as biopolyester polyol). Plant-derived fatty acids are fatty acids obtained from plant raw materials, and can be obtained, for example, by hydrolyzing vegetable oils. As a vegetable oil, the hydrogenated product (namely, hydrogenated vegetable oil) can also be used. As the plant-derived fatty acid, a hydrogenated product (that is, a hardened fatty acid) can also be used.

  Examples of vegetable oils include castor oil, soybean oil, palm oil, sesame oil, rapeseed oil, coconut oil, and hydrogenated products thereof. These vegetable oils can be used alone or in combination of two or more. The vegetable oil is preferably castor oil.

  The method for hydrolyzing vegetable oil is not particularly limited, and a known method is employed.

  The plant-derived fatty acid preferably contains a fatty acid containing a hydroxyl group (hereinafter sometimes referred to as a hydroxyl group-containing fatty acid).

  Examples of the hydroxyl group-containing fatty acid include hydroxyl group-containing monocarboxylic acids such as ricinoleic acid, 12-hydroxystearic acid and lactic acid, and hydroxyl group-containing dicarboxylic acids such as malic acid. These hydroxyl group-containing fatty acids can be used alone or in combination of two or more.

  From the viewpoint of reducing the viscosity during production of the biopolyester polyol (component (A)) and improving workability, the hydroxyl group-containing fatty acid is preferably a hydroxyl group-containing monocarboxylic acid, more preferably ricinoleic acid. Is mentioned.

  The content ratio of the hydroxyl group-containing fatty acid in the plant-derived fatty acid is, for example, 85 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more, based on the total amount of the plant-derived fatty acid. 100 mol% or less.

  When the content ratio of the hydroxyl group-containing fatty acid is within the above range, the capping of the molecular terminal hydroxyl group by the fatty acid not containing a hydroxyl group can be suppressed during the production of the component (A), so that a polyurethane foam having more excellent resilience can be obtained. .

  In addition, the content ratio of the hydroxyl group-containing fatty acid in the plant-derived fatty acid is obtained by analysis such as gas chromatography, but when a monoalcohol monocarboxylic acid is used as the hydroxyl group-containing fatty acid, JIS K-1557-1 (2007) ) And the hydroxyl value (OHV) of the hydroxyl group-containing fatty acid measured in accordance with the description of JIS K-1557-5 (2007). It is calculated | required by ratio (OHV / AV).

  The hydroxyl group-containing fatty acid contained in the plant-derived fatty acid is appropriately selected according to the type of vegetable oil used.

  For example, when castor oil is used as the vegetable oil, castor oil fatty acid obtained by hydrolysis thereof contains ricinoleic acid, which is a hydroxyl group-containing fatty acid, as a main component.

  The castor oil fatty acid contains, for example, unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid, and saturated fatty acids such as palmitic acid and stearic acid as other fatty acids.

  The content of each fatty acid in castor oil fatty acid is, for example, 87 to 90% by mass of ricinoleic acid, 2.5 to 4% by mass of oleic acid, and 4 to 5 of linoleic acid, based on the total mass of castor oil fatty acid. Mass%, linolenic acid is 0.5 to 1.5 mass%, palmitic acid is 0.5 to 1.5 mass%, and stearic acid is 0.5 to 1.5 mass%.

  When hydrogenated castor oil is used as the vegetable oil, the hydrogenated castor oil fatty acid obtained by hydrolysis thereof contains 12-hydroxystearic acid, which is a hydroxyl group-containing fatty acid, as a main component.

  On the other hand, when soybean oil, palm oil, sesame oil, rapeseed oil, coconut oil, and hydrogenated products thereof are used as vegetable oils, the fatty acid obtained by hydrolysis may not contain a hydroxyl group-containing fatty acid.

  In such a case, after hydrolyzing the vegetable oil, a hydroxyl group can be added to the resulting unsaturated fatty acid by a method such as air oxidation, epoxidation, or hydroformylation to obtain a hydroxyl group-containing fatty acid.

  These plant-derived fatty acids can be used alone or in combination of two or more.

  As the plant-derived fatty acid, castor oil fatty acid is preferably used from the viewpoint of ease of production.

  When the plant-derived fatty acid contains castor oil fatty acid, the content ratio of castor oil fatty acid is, for example, 50 mol% or more, preferably 70 mol% or more, more preferably 80 mol, based on the total amount of plant-derived fatty acid. % Or more, usually 100 mol% or less.

  If the plant-derived fatty acid contains castor oil fatty acid in the above-mentioned ratio, by using a biopolyester polyol (component (A)) obtained from the plant-derived fatty acid, hardness, elongation, tensile strength, tear strength, etc. A polyurethane foam having better mechanical properties can be obtained.

  Moreover, said plant-derived fatty acid (preferably castor oil fatty acid) can be refine | purified by well-known methods, such as distillation, extraction, and crystallization, for example.

  For example, when plant-derived fatty acids are distilled, known thin-film distillation apparatuses such as a rotating thin-film distillation apparatus and a falling thin-film distillation apparatus are used. From the viewpoint of evaporation efficiency, a rotating thin film distillation apparatus is preferable. The rotating thin film distillation apparatus is preferably used under high vacuum called molecular distillation. In addition, the distillation conditions are not particularly limited, but when castor oil fatty acid is used as the plant-derived fatty acid, in order to suppress its thermal decomposition and to suppress side reactions such as intramolecular dehydration, preferably, The distillation temperature is 180 ° C. or lower.

  Moreover, when a plant-derived fatty acid is extracted, it is not particularly limited, and an extraction method using a known extraction solvent is employed. The extraction solvent is not particularly limited, and is appropriately selected depending on the solubility of the plant-derived fatty acid, ease of solvent removal after extraction, and the like. For example, when a castor oil fatty acid is used as the plant-derived fatty acid, aliphatic hydrocarbons having 4 to 10 carbon atoms (such as hexane) are preferably used from the viewpoint of solubility. More specifically, the castor oil fatty acid and the extraction solvent are mixed in an appropriate ratio, and after separation by standing under any temperature condition, the extraction solvent phase and the castor oil fatty acid phase are separated, and then the castor oil fatty acid phase. The castor oil fatty acid can be purified by removing the extraction solvent partially dissolved in

  Moreover, said plant origin fatty acid can also be esterified and used by a well-known method, for example. More specifically, for example, the above plant-derived fatty acid and a low molecular weight monoalcohol (for example, methanol, ethanol, n-propanol, isopropanol, butanol, isobutanol, s-butanol, t-butanol, etc.) are used as an alkali catalyst. By reacting in the presence, the plant-derived fatty acid can be esterified.

  Moreover, said plant-derived fatty acid may be single-condensed (self-condensed) by a known method, for example. In other words, a plant-derived fatty acid that is single-condensed (self-condensed) can be used as a raw material for the biopolyester polyol.

  Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1, C2-C10 aliphatic dihydric alcohols such as 6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, such as 1,4-cyclohexanediol, 1,4-cyclohexane Aliphatic dihydric alcohols such as dimethanol, hydrogenated bisphenol A and hydrogenated bisphenol F, for example, aromatic dihydric alcohols such as bisphenol A and bisphenol F, for example, C 2-10 such as trimethylolpropane and glycerin A trihydric alcohol such as diglycerin Tetravalent alcohols such as pentaerythritol and α-methylglucoside, for example, hexavalent alcohols such as dipentaerythritol, for example, dextrose, glucose (pentahydric alcohol), sorbitol (hexavalent alcohol), fructose (pentahydric alcohol), shoe Examples thereof include saccharides such as claus (octavalent alcohol) and derivatives thereof, and phenols having 7 to 8 hydroxyl groups.

  In addition, as the polyhydric alcohol, a polyhydric alcohol obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to a part or all of the hydroxyl group (that is, an alkylene oxide adduct of a polyhydric alcohol) can also be used.

  These polyhydric alcohols can be used alone or in combination of two or more.

  Preferred examples of the polyhydric alcohol include 3 to 8 valent alcohols and their alkylene oxide adducts, more preferred examples include 4 to 6 valent alcohols and their alkylene oxide adducts, and even more preferred are pentaerythritol and its adducts. Examples include alkylene oxide adducts, sorbitol, and alkylene oxide adducts thereof.

  If the above polyhydric alcohol is used, an increase in the viscosity of the biopolyester polyol obtained can be suppressed, workability in the production of polyurethane foam can be improved, and the degree of crosslinking of the obtained polyurethane foam and The mechanical properties can be improved.

  The molecular weight of polyhydric alcohol (when an alkylene oxide adduct of polyhydric alcohol is used, the number average molecular weight (in terms of polyethylene glycol) measured by gel permeation chromatography (GPC) analysis) is, for example, 60 or more For example, it is 2000 or less, preferably 1000 or less.

  Moreover, the average functional group number of polyhydric alcohol is 3.5 or more, for example, Preferably, it is 4.5 or more, for example, is 8 or less, Preferably, it is 7 or less.

  If the average functional group number of the polyhydric alcohol is within the above range, an increase in the viscosity of the biopolyester polyol obtained using the polyhydric alcohol can be suppressed, and workability in the production of polyurethane foam can be improved. In addition, the degree of cross-linking and mechanical properties of the resulting polyurethane foam can be improved.

  In addition, the average functional group number of polyhydric alcohol is calculated from the preparation recipe of preparation.

  The hydroxyl value of the polyhydric alcohol is, for example, 100 mgKOH / g or more, preferably 150 mgKOH / g or more, more preferably 200 mgKOH / g or more, for example, 1200 mgKOH / g or less, preferably 800 mgKOH / g or less. More preferably, it is 600 mgKOH / g or less.

  The hydroxyl value can be measured according to the description of JIS K-1557-1 (2007) (the same applies hereinafter).

  And in order to obtain a component (A), the plant-derived fatty acid which may be condensed mentioned above, and a polyhydric alcohol are condensed by a well-known method, for example.

  Specifically, for example, in order to obtain a condensate of a non-condensed plant-derived fatty acid and a polyhydric alcohol, the non-condensed plant-derived fatty acid (monomer) is equimolar to the hydroxyl group of the polyhydric alcohol. It mix | blends so that it may become the following and it is made to condense.

  In order to obtain a condensed product of a plant-derived fatty acid and a polyhydric alcohol, for example, first, the plant-derived fatty acid is subjected to single condensation, and then the obtained plant-derived fatty acid single condensate and For example, a non-condensed plant-derived fatty acid (monomer) and a polyhydric alcohol are first subjected to a condensation reaction, and then condensed to the molecular end of the resulting condensate. Non-plant-derived fatty acid (monomer) may be further subjected to a condensation reaction.

  The component (A) preferably includes a condensed product of a condensed plant-derived fatty acid and a polyhydric alcohol. More preferably, first, a non-condensed plant-derived fatty acid (monomer) and a polyhydric alcohol are used. And a condensate obtained by further subjecting a non-condensed plant-derived fatty acid (monomer) to a condensation reaction at the molecular end of the resulting condensate.

  The blending ratio in such condensation of plant-derived fatty acid and polyhydric alcohol is appropriately set depending on the type of plant-derived fatty acid used, the average number of functional groups of the polyhydric alcohol, and the like.

  For example, when castor oil fatty acid is used as the plant-derived fatty acid and polyhydric alcohol having an average functional group number within the above range (for example, 3.5 or more and 8 or less) is used as the polyhydric alcohol, the total amount of polyhydric alcohol The blending amount of the plant-derived fatty acid is 100 parts by mass or more, preferably 500 parts by mass or more, for example, 10000 parts by mass or less, preferably 7000 parts by mass or less, more preferably 100 parts by mass. It is 5000 parts by mass or less.

  If the blending ratio of the plant-derived fatty acid and the polyhydric alcohol is within the above range, a polyurethane foam having more excellent physical properties can be obtained using the obtained component (A), and the environmental load due to the plant-derived fatty acid can be obtained. The reduction effect can be ensured more sufficiently.

  As the condensation reaction conditions, for example, in an inert gas atmosphere, the reaction temperature is, for example, 100 ° C. or higher, preferably 150 ° C. or higher, for example, 300 ° C. or lower, preferably 250 ° C. or lower. . The condensation reaction time is, for example, 5 hours or longer, preferably 10 hours or longer, for example, 200 hours or shorter, preferably 100 hours or shorter.

  In addition, in the condensation reaction, a known catalyst such as an organic titanium catalyst can be added at an appropriate ratio at an appropriate timing if necessary.

  In the component (A) thus obtained, the condensation ratio of the plant-derived fatty acid to the polyhydric alcohol is, for example, 1 mol or more, preferably 2 mol or more, per mol of the hydroxyl group of the polyhydric alcohol. 12 mol or less, preferably 8 mol or less.

  The number average molecular weight (in terms of polyethylene glycol) measured by gel permeation chromatography (GPC) analysis of the component (A) thus obtained is 300 or more, preferably 400 or more, for example, 5000 or less, Preferably, it is 3000 or less.

  Moreover, the average functional group number of a component (A) is 3.5 or more, for example, Preferably, it is 4.5 or more, for example, is 8 or less, Preferably, it is 7 or less.

  In addition, the average functional group number of a component (A) is computed from the preparation recipe of preparation.

  The hydroxyl value of component (A) is, for example, 15 mgKOH / g or more, preferably 25 mgKOH / g or more, more preferably 30 mgKOH / g or more, for example, 120 mgKOH / g or less, preferably 100 mgKOH / g. Hereinafter, it is more preferably 60 mgKOH / g or less.

  When the hydroxyl value of component (A) is in the above range, it is possible to shorten the curing time during the production of polyurethane foam, and to produce a polyurethane foam having better rebound resilience and hardness. Can do.

  Moreover, the acid value of a component (A) is 0 mgKOH / g or more, for example, is 3 mgKOH / g or less, for example, Preferably, it is 2 mgKOH / g or less.

  If the acid value of a component (A) is the said range, the outstanding reactivity can be ensured in manufacture of a polyurethane foam.

  In addition, the acid value of a component (A) can be measured based on the description of JIS K-1557-5 (2007) (hereinafter the same).

  Moreover, the viscosity at 25 degreeC of a component (A) is 500 mPa * s or more, for example, is 20000 mPa * s or less, Preferably, it is 15000 mPa * s or less, More preferably, it is 10000 mPa * s or less.

  If the viscosity of a component (A) is the said range, in the manufacture of a polyurethane foam, the outstanding workability | operativity can be ensured.

  In addition, the viscosity of a component (A) can be measured at 25 degreeC using a cone-plate type rotational viscometer (E-type viscometer) based on description of JIS K-1557-5 (2007). Yes (the same applies below).

  The polyether polyol (component (B)) is not particularly limited, and a known polyether polyol that is a petrochemical product can be used.

  More specifically, a polyalkylene polyol etc. are mentioned, for example.

  Examples of the polyalkylene polyol include alkylene oxides having the above-described polyhydric alcohols, low molecular weight polyamines (aliphatic polyamines (eg, ethylenediamine), aromatic polyamines (eg, tolylenediamine), etc.) as initiators, and the like. Addition polymers (including random and / or block copolymers of two or more alkylene oxides).

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, and allyl glycidyl ether. And alkylene oxides having 2 to 12 carbon atoms such as phenyl glycidyl ether.

  These alkylene oxides can be used alone or in combination of two or more.

  The alkylene oxide is preferably ethylene oxide, propylene oxide, 1,2-butylene oxide, or styrene oxide, more preferably ethylene oxide or propylene oxide.

  More specifically, examples of the polyalkylene polyol include polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide copolymer (random and / or block copolymer), and the like.

  Examples of the component (B) include a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran, for example, amorphous polytetramethylene ether glycol obtained by copolymerizing the above-described dihydric alcohol with a polymerization unit of tetrahydrofuran, for example, Polytetramethylene ether polyols such as amorphous polytetramethylene ether glycol obtained by copolymerizing ethylene oxide, propylene oxide, epichlorohydrin and / or benzyl glycidyl ether, etc., in the polymerized units of tetrahydrofuran are also included.

  The component (B) is preferably an ethylene oxide-propylene oxide copolymer.

  When an ethylene oxide-propylene oxide copolymer is used as the component (B), the terminal oxyethylene group content is, for example, 5% by mass or more, preferably 10% by mass or more, for example, 50% by mass or less. Preferably, it is 30 mass% or less.

  In addition, terminal oxyethylene group content rate is computed from the preparation recipe of preparation.

  The number average molecular weight (in terms of polyethylene glycol) measured by gel permeation chromatography (GPC) analysis of the component (B) is 300 or more, preferably 400 or more, for example, 15000 or less, preferably 10,000 or less. is there.

  Moreover, the average functional group number of a component (B) is 2.5 or more, for example, Preferably, it is 3 or more, for example, is 6 or less, Preferably, it is 4 or less.

  In addition, the average number of functional groups of the component (B) is calculated from the blended recipe.

  Further, the hydroxyl value of the component (B) is, for example, 10 mgKOH / g or more, preferably 15 mgKOH / g or more, more preferably 20 mgKOH / g or more, for example, 100 mgKOH / g or less, preferably 80 mgKOH / g. Hereinafter, it is more preferably 60 mgKOH / g or less.

  Moreover, the viscosity at 25 degreeC of a component (B) is 200 mPa * s or more, for example, is 5000 mPa * s or less, for example, Preferably, it is 3000 mPa * s or less.

  If the viscosity of a component (B) is the said range, in the manufacture of a polyurethane foam, the outstanding workability | operativity can be ensured.

  In the polyol composition of the present invention, the content ratio of the component (A) to the total amount of 100 parts by mass of the component (A) and the component (B) is, for example, 5 parts by mass or more, preferably 10 parts by mass or more. For example, it is 80 parts by mass or less, preferably 50 parts by mass or less. Moreover, the content rate of the component (B) with respect to 100 mass parts of total amounts of a component (A) and a component (B) is 20 mass parts or more, for example, Preferably, it is 50 mass parts or more, for example, 95 mass parts or less. The amount is preferably 90 parts by mass or less.

  If the content ratio of the component (A) and the component (B) is in the above range, a polyol composition capable of suppressing phase separation over a long period of time at a normal temperature and a relatively high temperature environment can be obtained. A polyurethane foam having more excellent physical properties can be obtained by using the polyol composition.

  Further, the polyol composition of the present invention can further contain other polyols (hereinafter also simply referred to as “other polyols”) excluding the component (A) and the component (B) as the polyol component.

  Other polyols include, for example, a low molecular weight polyol excluding component (A) and component (B) (hereinafter also simply referred to as “low molecular weight polyol”), a high molecular weight polyol excluding component (A) and component (B) ( Hereinafter, simply referred to as “high molecular weight polyol”).

  The low molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of 60 or more and less than 300, preferably less than 250, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butane. Diol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexacidiol, 3-methyl-1,5-pentanediol, 2- Methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, 1,3-dihydroxybenzene, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) ) Benzene, 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiph Nylmethane, 1,2 dihydroxycyclohexane, 1,3-dihydroxycyclohexane, 1,4-dihydroxycyclohexane, 1,2-dihydroxymethylcyclohexane, 1,3-dihydroxymethylcyclohexane, 1,4-dihydroxymethylcyclohexane, 1,2 -Bishydroxyethoxycyclohexane, 1,3-bishydroxyethoxycyclohexane, 1,4-bishydroxyethoxycyclohexane, 1,2-bishydroxyethoxycarbonylcyclohexane, 1,3-bishydroxyethoxycarbonylcyclohexane, 1,4-bishydroxy Ethoxycarbonylcyclohexane, 2,5-dihydroxymethylbicyclo [2.2.1] heptane, 2,6-dihydroxymethylbicyclo [2.2.1] hepta 3,8-dihydroxymethyl-tricyclo [5.2.2.02.6] decane, 3,9-dihydroxymethyl-tricyclo [5.2.1.02.6] decane, 4,8-dihydroxymethyl- Dihydric alcohols such as tricyclo [5.2.1.02.6] decane, glycerin, 2-hydroxymethyl-2-methyl-1,3-diol, 2-ethyl-2-hydroxymethyl-1,3-diol , 1,2,5-hexanetriol, 1,2,6-hexanetriol, 1,2,3-cyclohexanetriol, trivalent alcohols such as 1,3,5-cyclohexanetriol, pentaerythritol, glucose, sucrose, Fructose, sorbitol, 1,2,3,4-cyclohexanetetrol, 1,2,4,5-cyclohexanetetroe And tetrahydric or higher polyhydric alcohols such as cyclohexanepentol (quercitol), cyclohexanehexol (inositol), and xylitol.

  These low molecular weight polyols can be used alone or in combination of two or more.

  The high molecular weight polyol (excluding component (A) and component (B)) is a compound having two or more hydroxyl groups and a number average molecular weight of 300 or more, preferably 400 or more. Polyester polyols excluding biopolyester polyols), polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, and vinyl monomer-modified polyols.

  The petroleum-based polyester polyol is a known polyester polyol that is a petrochemical product, and examples thereof include polyester polyols obtained by reacting the above-described low molecular weight polyols with polybasic acids or acid anhydrides or acid halides thereof. It is done.

  Examples of the polybasic acid and its acid anhydride or its acid halide include oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3 -Methyl-3-ethylglutaric acid, azelaic acid, sebacic acid, other aliphatic dicarboxylic acids (C11-C13), hydrogenated dimer acid, maleic acid, fumaric acid, itaconic acid, orthophthalic acid, isophthalic acid, terephthalic acid , Carboxylic acids such as toluene dicarboxylic acid, dimer acid and het acid (dicarboxylic acid), and acid anhydrides derived from these carboxylic acids, such as oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride Acid, 2-alkyl anhydride (C12-C18) succinic acid, tetrahydrophthalic anhydride, trimellitic anhydride Acid, furthermore, the acid halide derived from such these carboxylic anhydrides, such as oxalic acid dichloride, adipic acid dichloride, and sebacic acid dichloride.

  Examples of petroleum polyester polyols include polycaprolactone polyols and polyvaleros obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone using the above low molecular weight polyol as an initiator. Examples include lactone polyester polyols such as lactone polyols.

  Examples of the polycarbonate polyol include polycarbonate polyols (preferably polycarbonate diols) obtained by condensation of the above-described low molecular weight polyols (preferably dihydric alcohols) with dicarbonates such as dimethyl carbonate and diethyl carbonate. .

  Further, as the polycarbonate polyol, for example, a ring-opening polymer of ethylene carbonate having the above-described low molecular weight polyol (preferably a dihydric alcohol) as an initiator, for example, 1,4-butanediol, 1,5-pentanediol And amorphous polycarbonate polyols obtained by copolymerizing a dihydric alcohol such as 3-methyl-1,5-pentanediol or 1,6-hexanediol with a ring-opening polymer.

  Furthermore, examples of the polycarbonate polyol include plant-derived polycarbonate polyols, and specifically, alicyclic dihydroxy compounds such as isosorbide derived from plant-derived raw materials such as glucose, and the above-described low molecular polyols (preferably Is a polycarbonate polyol obtained by subjecting a dihydric alcohol) to a transesterification reaction with diphenyl carbonate.

  The polyurethane polyol is at least one selected from the group consisting of the above-mentioned polyester polyols (biopolyester polyols, petroleum-based polyester polyols), polyether polyols and polycarbonate polyols, and the equivalent ratio of hydroxyl groups to isocyanate groups (OH / NCO) is 1. Can be obtained as a polyester polyurethane polyol, a polyether polyurethane polyol, a polycarbonate polyurethane polyol, a polyester polyether polyurethane polyol or the like by reacting with a polyisocyanate component described later at a ratio exceeding.

  Examples of the epoxy polyol include an epoxy polyol obtained by a reaction of the above-described low molecular weight polyol with a polyfunctional halohydrin such as epichlorohydrin or β-methylepichlorohydrin.

  Examples of the vegetable oil polyol include hydroxyl group-containing vegetable oils such as castor oil and modified coconut oil. For example, castor oil polyol can be used.

  Examples of the polyolefin polyol include polybutadiene polyol and partially saponified ethylene-vinyl acetate copolymer.

  Examples of the acrylic polyol include a copolymer obtained by copolymerizing a hydroxyl group-containing acrylate and a copolymerizable vinyl monomer copolymerizable with the hydroxyl group-containing acrylate.

  Examples of the hydroxyl group-containing acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,2-dihydroxymethylbutyl (meth) acrylate, polyhydroxyalkyl maleate, poly And hydroxyalkyl fumarate. Preferably, 2-hydroxyethyl (meth) acrylate etc. are mentioned.

  Examples of the copolymerizable vinyl monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and s-butyl ( (Meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl acrylate, isobornyl (meth) ) Alkyl (meth) acrylates such as acrylate (C1-12), for example, aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, for example (meth) acrylic Vinyl cyanides such as nitriles, for example, vinyl monomers containing carboxyl groups such as (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, or alkyl esters thereof, such as ethylene glycol di (meth) acrylate, butylene glycol Alkane polyol poly (meth) acrylates such as di (meth) acrylate, hexanediol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, For example, a vinyl monomer containing an isocyanate group such as 3- (2-isocyanate-2-propyl) -α-methylstyrene can be used.

  The acrylic polyol can be obtained by copolymerizing these hydroxyl group-containing acrylate and copolymerizable vinyl monomer in the presence of a suitable solvent and a polymerization initiator.

  The acrylic polyol includes, for example, silicone polyol and fluorine polyol.

  Examples of the silicone polyol include an acrylic polyol in which a silicone compound containing a vinyl group such as γ-methacryloxypropyltrimethoxysilane is blended as the copolymerizable vinyl monomer in the copolymerization of the acrylic polyol described above. .

  As the fluorine polyol, for example, in the copolymerization of the acrylic polyol described above, as the copolymerizable vinyl monomer, for example, an acrylic polyol in which a fluorine compound containing a vinyl group such as tetrafluoroethylene or chlorotrifluoroethylene is blended may be mentioned. .

  The vinyl monomer-modified polyol (polymer polyol) can be obtained by reacting a vinyl monomer in a high molecular weight polyol.

  The high molecular weight polyol is a dispersion medium of a vinyl monomer, and includes a known high molecular weight polyol. Specifically, for example, the above-described polyether polyol, the above-described polyester polyol, the above-described polycarbonate polyol and the like can be mentioned.

  Examples of the vinyl monomer include styrene, acrylamide, alkyl (meth) acrylate, vinyl cyanide (acrylonitrile), vinylidene cyanide, and the like. These vinyl monomers can be used alone or in combination of two or more. Of these, vinyl cyanide (acrylonitrile) is preferable.

  The vinyl monomer-modified polyol is obtained by converting these high molecular weight polyol and vinyl monomer into, for example, radical polymerization initiators (for example, persulfates, organic peroxides, azo compounds (azobisisobutyronitrile, etc.), etc. ), And in the presence of a dispersion stabilizer, a chain transfer agent, and the like.

  More specifically, the vinyl monomer-modified polyol is prepared by polymerizing the above vinyl monomer with a radical initiator in a high molecular weight polyol and dispersing the resulting polymer fine particles in the high molecular weight polyol.

  The polymer fine particles may be polymer fine particles made of a polymer of vinyl monomer, and at the time of polymerization, at least a part of the vinyl monomer is a high molecular weight polyol (specifically, a high molecular weight polyol having an ethylenically unsaturated bond). The polymer fine particles may be grafted to the polymer. Preferably, polymer fine particles in which at least a part of a vinyl monomer is grafted to a high molecular weight polyol at the time of polymerization are exemplified.

  These high molecular weight polyols can be used alone or in combination of two or more.

  These other polyols can be used alone or in combination of two or more.

  The other polyols preferably include high molecular weight polyols, and more preferably vinyl monomer-modified polyols.

  When the polyol composition of the present invention contains other polyols, the content ratio thereof is, for example, 1 part by mass or more, preferably 5 parts by mass or more, with respect to 100 parts by mass of the total amount of polyol components. 80 parts by mass or less, preferably 50 parts by mass or less, and more preferably 45 parts by mass or less.

  If the content ratio of other polyols is in the above range, the effect of reducing the environmental load can be more sufficiently ensured.

  When the polyol composition of the present invention contains other polyol, the content ratio of the component (A) is, for example, 8 parts by mass or more, preferably 10 parts by mass with respect to 100 parts by mass of the total amount of the polyol components. As mentioned above, More preferably, it is 20 mass parts or more, for example, 80 mass parts or less, Preferably, it is 70 mass parts or less. Moreover, the content rate of a component (B) is 10 mass parts or more with respect to 100 mass parts of total amounts of a polyol component, Preferably, it is 20 mass parts or more, for example, 80 mass parts or less, Preferably, it is 75. It is below mass parts.

  If the content rate of a component (A) and a component (B) is the said range, an environmental impact reduction effect can be ensured more fully.

  The polyol composition of the present invention contains a polyoxyethylene adduct of a hydroxyl group-containing fatty acid ester (component (C)) as a phase separation inhibitor.

  The hydroxyl group-containing fatty acid ester can be obtained by esterifying a hydroxyl group-containing fatty acid and at least one selected from the group consisting of monohydric alcohols and polyhydric alcohols by a known method.

  Examples of the hydroxyl group-containing fatty acid include hydroxyl group-containing monocarboxylic acids such as lactic acid, glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, γ-hydroxybutyric acid, ricinoleic acid, 12-hydroxystearic acid, hydroxyundecanoic acid, and cerebronic acid. , Hydroxyl group-containing dicarboxylic acids such as malic acid and tartaric acid.

  These hydroxyl group-containing fatty acids can be used alone or in combination of two or more.

  The hydroxyl group-containing fatty acid is preferably a hydroxyl group-containing monocarboxylic acid, more preferably ricinoleic acid or 12-hydroxystearic acid.

  Examples of the monohydric alcohol include methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, n-undecanol, n -Dodecanol (lauryl alcohol), n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol (stearyl alcohol), n-nonadecanol, eicosanol Linear monohydric alcohol such as isopropanol, isobutanol, sec-butanol, tert-butanol, isopentanol, isohexanol, isoheptanol, isooctanol, 2-ethylhexan-1-ol, isononanol Isodecanol, 5-ethyl-2-nonanol, trimethylnonyl alcohol, 2-hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol, 2-octyldodecanol, other branched alkanols (carbon Examples thereof include branched monohydric alcohols such as formulas 5 to 20). These monohydric alcohols can be used alone or in combination of two or more.

  As polyhydric alcohol, the polyhydric alcohol similar to the polyhydric alcohol used for manufacture of above-mentioned biopolyester polyol is mentioned. Polyhydric alcohols can be used alone or in combination of two or more.

  As at least one selected from the group consisting of monohydric alcohols and polyhydric alcohols, preferably, polyhydric alcohols are mentioned, more preferably, 2- to 4-valent alcohols are mentioned, and still more preferably, trivalent alcohols are mentioned. Particularly preferred is glycerin.

  That is, the hydroxyl group-containing fatty acid ester is preferably a glyceride of the hydroxyl group-containing fatty acid.

  Examples of glycerides of hydroxyl group-containing fatty acids include monoglycerides of hydroxyl group-containing fatty acids, diglycerides of hydroxyl group-containing fatty acids, triglycerides of hydroxyl group-containing fatty acids, and preferably triglycerides of hydroxyl group-containing fatty acids.

  The hydroxyl group-containing fatty acid ester (preferably a triglyceride of a hydroxyl group-containing fatty acid) preferably contains a vegetable oil, more preferably contains at least one selected from the group consisting of castor oil and hydrogenated products thereof, more preferably castor oil. Of hydrogenated products (hereinafter also referred to as hardened castor oil).

  If the hydroxyl group-containing fatty acid ester contains hydrogenated castor oil (in other words, if the hydroxyl group-containing fatty acid ester polyoxyethylene adduct contains a hydrogenated castor oil polyoxyethylene adduct), the affinity with the biopolyester polyol As a result, the effect of suppressing the phase separation can be further improved.

  The polyoxyethylene adduct of the hydroxyl group-containing fatty acid ester (component (C)) is not particularly limited, but ethylene oxide is added by a known method using the hydroxyl group-containing fatty acid ester (preferably, hardened castor oil) as a starting material. Can be obtained.

  In component (C), the average number of moles of ethylene oxide added (hereinafter also referred to as “p”) is, for example, 40 or more, preferably 45 or more, per 1 mol of a hydroxyl group-containing fatty acid ester (preferably hardened castor oil). More preferably, it is 55 or more, for example, 150 or less, preferably 120 or less, more preferably 100 or less.

  In the component (C), when p is in the above range, phase separation can be suppressed over a longer period at room temperature and a relatively high temperature environment, and the viscosity increase of the polyol composition can be further suppressed. it can.

  The polyol composition of the present invention preferably contains a plurality of components (C) having different average added mole numbers of ethylene oxide.

  If the polyol composition contains a plurality of components (C) having different average addition mole numbers of ethylene oxide, the content ratio of the biopolyester polyol is, for example, as high as 20% by mass or more based on the total amount of the polyol components. Even if it is a case, phase separation can be suppressed favorably.

Such a polyol composition includes, for example, a polyoxyethylene adduct of a hydroxyl group-containing fatty acid ester having an average addition mole number of ethylene oxide of p _S (hereinafter also referred to as component (C _S )) and an average addition mole of ethylene oxide. number polyoxyethylene adducts of hydroxyl-containing fatty acid ester is a great p _L than p _S (hereinafter, also referred to as component (C _L).) the two types of the polyoxyethylene adducts of hydroxyl-containing fatty acid esters, Contains at least.

More preferably, the polyol composition of the present invention comprises at least component (A), component (B), component (C _S ), and component (C _L ).

In such a case, p _S and p _L are both 40 or more, preferably 45 or more, more preferably 55 or more, for example 150 or less, preferably 120 or less, more preferably 100 or less.

Further, the difference between p _S and p _L (p _L −p _S ) is, for example, 10 or more, preferably 15 or more, more preferably 20 or more, for example 60 or less, preferably 50 or less, more preferably 40 or less. It is.

In the present specification, the average added mole number of ethylene oxide in the component (C), the component (C _S ) and the component (C _L ) means the average added mole number of ethylene oxide with respect to 1 mole of the hydroxyl group-containing fatty acid ester. .

The content ratio of the component (C _S ) and the component (C _L ) is such that the component (C _S ) is, for example, 10 parts by mass or more, preferably 20 parts by mass or more with respect to the total amount of 100 parts by mass. Yes, for example, 85 parts by mass or less, preferably 75 parts by mass or less. The component (C _L ) is, for example, 15 parts by mass or more, preferably 25 parts by mass or more, for example, 90 parts by mass or less, preferably 80 parts by mass or less.

Further, the difference between the content ratio of the component (C _S ) and the content ratio of the component (C _L ) is, for example, 0 part by mass or more, for example, 80 parts by mass or less, preferably 70 parts by mass or less. More preferably, it is 60 parts by mass or less.

Further, the polyol composition of the present invention, the component (A), component (B), and the component _{(C S),} when the component _{(C L),} formed by at least mixing, the component _(C S) And the proportion of the component (C _L ) is preferably the same as the proportion of the component (C _S ) and the component (C _L ).

As the component (C), is not limited to two components _{(C S)} and the component _{(C L),} for example, the average addition mole number of ethylene oxide is a small _{p M} than large _{p L} than _{p S} A polyoxyethylene adduct (component (C _M )) of a certain hydroxyl group-containing fatty acid ester and the like can be further blended at an appropriate ratio.

  In addition, the average number of functional groups of the component (C) thus obtained is, for example, 1 or more, preferably 2 or more, for example, 6 or less, preferably 4 or less.

  Note that the average number of functional groups is calculated from the blended recipe.

  The hydroxyl value of component (C) is, for example, 20 mgKOH / g or more, preferably 25 mgKOH / g or more, more preferably 30 mgKOH / g or more, for example, 60 mgKOH / g or less, preferably 55 mgKOH / g or less, More preferably, it is 50 mgKOH / g or less.

  The polyol composition of the present invention further contains, as a phase separation inhibitor, other phase separation inhibitors excluding component (C) (hereinafter also simply referred to as “other phase separation inhibitors”). Can do.

  When the polyol composition contains another phase separation inhibitor, the content ratio of the component (C) is, for example, 80 parts by mass or more, preferably 95 parts by mass with respect to 100 parts by mass of the total amount of the phase separation inhibitor. Part or more and 100 parts by weight or less.

  When the content ratio of the component (C) is in the above range, a polyol composition in which phase separation is suppressed over a longer period at room temperature and a relatively high temperature environment can be obtained, and the polyol composition is used. Thus, a polyurethane foam having better mechanical properties can be obtained.

  The phase separation inhibitor preferably does not contain other phase separation inhibitors. In other words, the phase separation inhibitor preferably consists only of component (C).

  The hydroxyl value of the phase separation inhibitor is, for example, 20 mgKOH / g or more, preferably 25 mgKOH / g or more, more preferably 30 mgKOH / g or more, for example, 60 mgKOH / g or less, preferably 55 mgKOH / g. Hereinafter, more preferably, it is 50 mgKOH / g or less.

  If the hydroxyl value of the phase separation inhibitor is in the above range, a polyol composition in which phase separation is suppressed over a longer period of time at a normal temperature and a relatively high temperature environment can be obtained, and the polyol composition is used. Thus, a polyurethane foam having better mechanical properties can be obtained.

  And a polyol composition can be obtained by mix | blending and mixing said polyol component and said phase-separation inhibitor.

  In the polyol composition, the content ratio of the polyol component with respect to 100 parts by mass of the total amount of the polyol component and the phase separation inhibitor is, for example, 85 parts by mass or more, preferably 90 parts by mass or more, more preferably 93 parts by mass or more. For example, it is 99.9 parts by mass or less, preferably 99.5 parts by mass or less, and more preferably 99 parts by mass or less.

  Moreover, the content ratio of the phase separation inhibitor with respect to 100 parts by mass of the total amount of the polyol component and the phase separation inhibitor is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, more preferably 1 part by mass. For example, it is 15 parts by mass or less, preferably 10 parts by mass or less, and more preferably 7 parts by mass or less.

  In the polyol composition, the content ratio of the component (A) with respect to 100 parts by mass of the total amount of the polyol component and the phase separation inhibitor is, for example, 2 parts by mass or more, preferably 5 parts by mass or more, more preferably 8 parts. For example, 60 parts by mass or less, preferably 50 parts by mass or less, more preferably 30 parts by mass or less.

  When the content ratio of the component (A) is in the above range, an environmental load can be reduced, and a polyol composition in which phase separation is suppressed for a longer period at room temperature and a relatively high temperature environment is obtained. In addition, a polyurethane foam having more excellent mechanical properties can be obtained using the polyol composition.

  In the polyol composition, the content ratio of the component (B) with respect to 100 parts by mass of the total amount of the polyol component and the phase separation inhibitor is, for example, 10 parts by mass or more, preferably 15 parts by mass or more. It is 90 parts by mass or less, preferably 90 parts by mass or less.

  When the content ratio of the component (B) is in the above range, an environmental load can be reduced, and a polyol composition in which phase separation is suppressed for a longer period at room temperature and a relatively high temperature environment is obtained. In addition, a polyurethane foam having more excellent mechanical properties can be obtained using the polyol composition.

  In the polyol composition, the content ratio of the component (C) with respect to 100 parts by mass of the total amount of the polyol component and the phase separation inhibitor is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more. The amount is preferably 1 part by mass or more, for example, 15 parts by mass or less, preferably 10 parts by mass or less, more preferably 7 parts by mass or less.

  If the content ratio of the component (C) is in the above range, an environmental load can be reduced, and a polyol composition in which phase separation is suppressed for a longer period at room temperature and a relatively high temperature environment is obtained. In addition, a polyurethane foam having more excellent mechanical properties can be obtained using the polyol composition.

  And since such a polyol composition contains the polyoxyethylene adduct (component (C)) of a hydroxyl-containing fatty acid ester as a phase separation inhibitor, biopolyester polyol (component (A)) and petrochemical Even when the product polyether polyol (component (B)) is mixed, phase separation can be suppressed over a long period of time at room temperature and at a relatively high temperature. Moreover, if such a polyol composition is used, a polyurethane foam having excellent mechanical properties can be obtained.

  Examples of the polyurethane foam include a flexible polyurethane foam and a rigid polyurethane foam, and preferably a flexible polyurethane foam.

  The polyurethane foam can be obtained by reacting the above polyol composition with the polyisocyanate component.

  Examples of the polyisocyanate component include polyisocyanate monomers and polyisocyanate derivatives.

  Examples of the polyisocyanate monomer include aromatic polyisocyanate, araliphatic polyisocyanate, and aliphatic polyisocyanate.

  Examples of the aromatic polyisocyanate include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4, 4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof) (MDI), Examples include aromatic diisocyanates such as 4,4′-toluidine diisocyanate (TODI) and 4,4′-diphenyl ether diisocyanate.

  Examples of the araliphatic polyisocyanate include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetra). Methyl xylylene diisocyanate or a mixture thereof (TMXDI), aromatic aliphatic diisocyanates such as ω, ω′-diisocyanate-1,4-diethylbenzene, and the like.

  Examples of the aliphatic polyisocyanate include ethylene diisocyanate, trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate. ), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capate And aliphatic diisocyanates such as dodecamethylene diisocyanate.

Aliphatic polyisocyanates include alicyclic polyisocyanates. Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), and 3-isocyanatomethyl-3. , 5,5-trimethylcyclohexylisocyanate (isophorodiisocyanate) (IPDI), methylenebis (cyclohexylisocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis (cyclohexylisocyanate, these Trans, Trans - body, Trans, Cis body, Cis, Cis body, or mixtures _thereof)) (H 12 _MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane Isocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (NBDI), bis (isocyanatomethyl) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) cyclohexane Or a mixture thereof) (H ₆ XDI) and the like.

  These polyisocyanate monomers can be used alone or in combination of two or more.

  Examples of the polyisocyanate derivative include a multimer (for example, dimer, trimer (for example, isocyanurate-modified product, iminooxadiazinedione-modified product), pentamer, 7) of the polyisocyanate monomer described above. ), Allophanate-modified products (for example, allophanate-modified products produced from the reaction of the above-mentioned polyisocyanate monomer and low molecular weight polyol), polyol-modified products (for example, the above-mentioned polyisocyanate monomer and low Polyol-modified products (alcohol adducts, etc.) produced by reaction with molecular weight polyols), biuret-modified products (for example, biuret-modified products produced by reaction of the above-mentioned polyisocyanate monomer with water or amines), Urea modified products (for example, in the reaction of the above polyisocyanate monomer and diamine) Modified urea-modified products), oxadiazine trione-modified products (for example, oxadiazine trione produced by reaction of the above-mentioned polyisocyanate monomer and carbon dioxide gas), carbodiimide-modified products (such as the above-mentioned polyisocyanate single product). Carbodiimide-modified products produced by decarboxylation condensation reaction of monomers), uretdione-modified products, uretonimine-modified products, and the like.

  Furthermore, examples of the polyisocyanate derivative include polymethylene polyphenylene polyisocyanate (crude MDI, polymeric MDI).

  These polyisocyanate derivatives can be used alone or in combination of two or more.

  The polyisocyanate component is preferably an aromatic polyisocyanate and a derivative thereof, more preferably tolylene diisocyanate and polymethylene polyphenylene polyisocyanate (crude MDI, polymeric MDI), and more preferably a combination thereof. Is mentioned.

  When tolylene diisocyanate and polymethylene polyphenylene polyisocyanate are used in combination, their blending ratio is, for example, tolylene diisocyanate is 100 parts by mass of tolylene diisocyanate and polymethylene polyphenylene polyisocyanate, 50 parts by mass or more, preferably 70 parts by mass or more, for example, 90 parts by mass or less, preferably 85 parts by mass or less. Moreover, polymethylene polyphenylene polyisocyanate is 10 mass parts or more, for example, Preferably, it is 15 mass parts or more, for example, 50 mass parts or less, Preferably, it is 30 mass parts or less.

  These polyisocyanate components can be used alone or in combination of two or more.

  In order to produce a polyurethane foam, first, a premix (resin premix) is prepared by blending various additives such as a catalyst, a crosslinking agent, a foaming agent, and a foam stabilizer, if necessary, with the above-described polyol composition. ) Is prepared.

  That is, the polyol composition of the present invention can contain various additives such as a catalyst, a crosslinking agent, a foaming agent, and a foam stabilizer, in addition to the above-described polyol component and phase separation inhibitor, as a premix. Can be prepared.

  As the catalyst, a known urethanization catalyst can be used. Specifically, for example, triethylenediamine, bis- (2-dimethylaminoethyl) ether, 1-isobutyl-2-methylimidazole, morpholines, etc. Aliphatic amines, for example, organotin compounds such as tin octoate and dibutyltin dilaurate are mentioned.

  Moreover, a catalyst can be obtained as a commercial item, for example, Kao Riser No. 31 (amine catalyst, manufactured by Kao Corporation), Kao Riser No. 120 (amine catalyst, 1-isobutyl-2-methylimidazole, manufactured by Kao Corporation), Kao Riser No. 12 (amine catalyst, manufactured by Kao Corporation), Neostan U-100 (organic tin compound, dibutyltin dilaurate, manufactured by Nitto Kasei Corporation), and the like.

  These catalysts can be used alone or in combination of two or more.

  The blending ratio of the catalyst is, for example, 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyol component in the polyol composition.

  The cross-linking agent is not particularly limited, and examples thereof include known cross-linking agents, and specifically include alkanolamines.

  Examples of the alkanolamine include polyalkanolamines such as trialkanolamines such as trimethanolamine, triethanolamine, tripropanolamine, triisopropanolamine, and tributanolamine, and dialkanolamines such as diethanolamine.

  These alkanolamines can be used alone or in combination of two or more.

  In addition to the alkanolamine, examples of the crosslinking agent include the above low molecular weight polyols such as glycerin and trimethylolpropane and / or alkylene oxide addition polyols thereof.

  As a crosslinking agent, Preferably, low molecular weight polyol and / or its alkylene oxide addition polyol are mentioned.

  Moreover, as a crosslinking agent, Preferably, the compound whose hydroxyl value is 200-1800 mgKOH / g is mentioned, More preferably, the polyoxyalkylene polyol (for example, Mitsui Chemicals make, a hydroxyl value is 200-1800 mgKOH / g) is mentioned. Actol KL-210: Polyoxyalkylene polyol having a functional group number of 3.75, OHV = 840 mgKOH / g).

  The mixture ratio of a crosslinking agent is 0.5-10 mass parts with respect to 100 mass parts of polyol components in a polyol composition, for example.

  It does not restrict | limit especially as a foaming agent, A well-known foaming agent is mentioned, Preferably water is mentioned.

  As the foaming agent, water and a physical foaming agent (for example, hydrofluorocarbons, hydrocarbons (cyclopentane, etc.), carbon dioxide gas, liquefied carbon dioxide gas, etc.) can be used in an appropriate ratio. The physical foaming agent is preferably carbon dioxide gas or liquefied carbon dioxide gas from the viewpoint of reducing environmental burden.

  The blending ratio of the foaming agent is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, for example, 30.0 parts by mass or less, with respect to 100 parts by mass of the polyol component in the polyol composition. The amount is preferably 20.0 parts by mass or less.

  In particular, when water is used as the blowing agent, the mixing ratio of water is, for example, 1.3 parts by mass or more, preferably 1.8 parts by mass or more, with respect to 100 parts by mass of the polyol component in the polyol composition. More preferably, it is 2.0 parts by mass or more, for example, 6.0 parts by mass or less, preferably 5.0 parts by mass or less, and more preferably 4.0 parts by mass or less.

  If the content rate of the water as a foaming agent is the said range, the outstanding foamability can be obtained.

  It does not restrict | limit especially as a foam stabilizer, A well-known foam stabilizer is mentioned.

  Moreover, a foam stabilizer can be obtained as a commercial item, for example, SZ-1966 (made by Toray Dow Corning), SRX-274C, SF-2969, SF-2961, SF-2962, L-5309, L-3601, L-5307, L-3600, L-5366, SZ-1325, SZ-1328, Y-10366 (manufactured by Momentive) and the like.

  These foam stabilizers can be used alone or in combination of two or more.

  The blending ratio of the foam stabilizer is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, for example, 10 parts by mass or less, with respect to 100 parts by mass of the polyol component in the polyol composition. Preferably, it is 5 parts by mass or less.

  In addition to the above components, the preparation of the premix is also known, for example, as a communicator, further a chain extender, a flame retardant, a pigment, an ultraviolet absorber, an antioxidant, an antifoaming agent, etc. These additives can be blended at an appropriate ratio as long as the excellent effects of the present invention are not impaired.

  Next, the premix thus obtained and the polyisocyanate component are mixed.

  The blending ratio of the polyisocyanate component is, for example, an isocyanate index (hydroxyl group in the polyol component in the premix, hydroxyl group and amino group in the crosslinking agent, ratio of isocyanate group to active hydrogen 100 such as water as a blowing agent (stoichiometry). As a ratio)), for example, 70 or more, preferably 80 or more, more preferably 90 or more, still more preferably 94 or more, for example, 130 or less, preferably 120 or less, more preferably 110 or less, More preferably, it is 108 or less.

  When the isocyanate index is in the above range, a polyurethane foam having excellent mechanical properties (such as hardness, mechanical strength, impact resilience, elongation rate, moldability, etc. excellent in cushioning properties) can be obtained.

  And while making a premix and a polyisocyanate component react, it is made to foam by well-known foaming systems, such as a slab system, a mold system, and a spray system, for example. Thereby, a polyurethane foam can be obtained.

  Since the polyurethane foam obtained in this way uses biopolyester polyol obtained by condensation of plant-derived fatty acid and polyhydric alcohol as a raw material component, it can cope with carbon neutral and reduce the burden on the global environment. Can do.

  Further, the polyurethane foam obtained in this way has excellent mechanical properties because the above-described polyol composition is used as a raw material component.

  More specifically, the obtained polyurethane foam is excellent in durability, and wet heat compression set (wet set) (according to JIS K-6400 (1997)) is, for example, 20% or less, preferably, 15% or less, more preferably 10% or less, usually 5% or more.

  If the wet heat compression set is in the above range, excellent durability can be provided in a wet heat environment.

The density of the polyurethane foam (conforming to JIS K-6400 (1997)) is, for example, 15 kg / m ³ or more, preferably 25 kg / m ³ or more, for example, 100 kg / m ³ or less, preferably 70 kg / m ³ or less.

  The tensile strength (based on JIS K-6400 (1997)) of the polyurethane foam is, for example, 80 kPa or more, preferably 100 kPa or more, for example, 500 kPa or less, preferably 400 kPa or less.

  The elongation of the polyurethane foam (conforming to JIS K-6400 (1997)) is, for example, 60% or more, preferably 80% or more, for example, 300% or less, preferably 200% or less. .

  The tear strength of the polyurethane foam (based on JIS K-6400 (1997)) is, for example, 4 N / cm or more, preferably 4.5 N / cm or more, for example, 10 N / cm or less, preferably 8 N / cm or less.

  Such a polyurethane foam can be suitably used as an impact absorbing material, a sound absorbing material, a vibration absorbing material, a body pressure dispersing material or the like.

  In addition, although the case where a polyol composition was used for manufacture of a polyurethane foam was demonstrated, the use of a polyol composition is not limited to the above, It can use for manufacture of a well-known polyurethane resin.

  Examples of polyurethane resins include elastomers (polyurethane solutions, water-based polyurethanes, hot melt molding (slush molding, rotational molding) urethane powder, thermoplastic urethane elastomers (TPU), thermosetting urethane elastomers (TSU), spray molded urethanes, and melts. Spinning or dry spinning elastic fiber), paint (mainly solution-based, powder-based curing agents: adduct, allophanate, burette, uretdione, polyisocyanurate, iminooxadiandione and mixtures thereof), industrial or hot melt Adhesives, sealing materials, gels and the like.

Next, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited by the following Example. In the following description, “part” and “%” are based on mass unless otherwise specified. In addition, the numerical value of the Example shown below can be substituted to the corresponding numerical value (namely, upper limit value or lower limit value) described in embodiment.
<Measurement method>
(1) Hydroxyl value (OHV)
It was measured by the method described in JIS K-1557-1 (2007).

(2) Number average molecular weight (Mn)
About 0.05 g of a sample having a number average molecular weight was precisely weighed, and tetrahydrofuran (hereinafter abbreviated as “THF”) was added to make up to 10 mL. This was measured under the following conditions using gel permeation chromatography (GPC) HLC-8020 (manufactured by Tosoh Corporation).

Eluent: THF
Eluent flow rate: 0.8ml / min
Eluent temperature: 40 ° C
Column temperature: 40 ° C
Column: Tosoh TSKgel G-3000H, G-2000H, G-1000H connected in series Detector: RI
Standard sample: Polyethylene glycol (3) Acid value Measurement was carried out by the method described in JIS K-1557-5 (2007).

(4) Viscosity Based on the description of JIS K-1557 (2007), the viscosity at 25 ° C. was measured using a conical plate type rotational viscometer (E type viscometer).

(5) Purity of castor oil fatty acid The content ratio of the hydroxyl group-containing fatty acid in the castor oil fatty acid was measured as the purity of the castor oil fatty acid.

  Specifically, the purity of castor oil fatty acid is determined by the hydroxyl value (OHV) of castor oil fatty acid measured by the method of JIS K-1557-1 (2007) and the method of JIS K-1557-5 (2007). It calculated | required by ratio (OHV / AV) with the acid value (AV) of the castor oil fatty acid measured.

<Description of phase separation inhibitor>
(Phase separation inhibitor C1)
The product name Emanon CH-80 (polyoxyethylene 80 mol adduct of hardened castor oil, hydroxyl value 37.7 mg KOH / g, HLB 15.3, manufactured by Kao Corporation (hereinafter the same)) was designated as phase separation inhibitor C1.

(Phase separation inhibitor C2)
Trade name Emanon CH-60K (Polyoxyethylene 60 mol adduct of hydrogenated castor oil, hydroxyl value 46.0 mg KOH / g, HLB 14.0, manufactured by Kao Corporation (hereinafter the same)) 33% by mass, Emanon CH-80 67% by mass And a mixed product (hydroxyl value: 40.5 mgKOH / g) as a phase separation inhibitor C2.

(Phase separation inhibitor C3)
Emanon CH-60K was designated as phase separation inhibitor C3.

(Phase separation inhibitor C4)
Dimethyl palmitylamine was added as a catalyst to 1 mol of trimethylolpropane, and propylene oxide was subjected to addition polymerization at a reaction temperature of 115 ° C. and a maximum reaction pressure of 5.0 kg / cm ² to obtain a polyether polyol having a hydroxyl value of 875 mgKOH / g. . This was designated as phase separation inhibitor C4.

(Phase separation inhibitor C5)
The trade name R-45HT (polybutadiene polyol, manufactured by Idemitsu Kosan Co., Ltd.) was designated as phase separation inhibitor C5.

(Phase separation inhibitor C6)
Product name R-15HT (polybutadiene polyol, manufactured by Idemitsu Kosan Co., Ltd.) was designated as phase separation inhibitor C6.

(Phase separation inhibitor C7)
Emanon CH-80 50% by mass and trade name UNIOX HC-100 (100 mol of polyoxyethylene adduct of hardened castor oil, hydroxyl value 33.5 mg KOH / g, HLB 16.6, manufactured by NOF Corporation (hereinafter the same)) 50 A mixed product with a mass% (hydroxyl value 35.6 mgKOH / g) was designated as phase separation inhibitor C7.

(Phase separation inhibitor C8)
A mixture of 50% by mass of Emanon CH-60K and 50% by mass of UNIOX HC-100 (hydroxyl value 39.8 mgKOH / g) was designated as phase separation inhibitor C8.

(Phase separation inhibitor C9)
The product name Emulgen 935 (nonylphenol polyoxyethylene 35 mol adduct, HLB 17.5, manufactured by Kao Corporation) was designated as phase separation inhibitor C9.

(Phase separation inhibitor C10)
Trade name Emulgen _{1135S-70 (C 11-13} polyoxyethylene 35 mol adduct of branched alkyl alcohol, HLB17.9, effective component 70 mass%, manufactured by Kao Corporation) was a phase separation inhibitor C10.

(Phase separation inhibitor C11)
The product name Rheodor 460V (polyoxyethylene 60 mol adduct of sorbite tetraoleate, HLB13.8, manufactured by Kao Corporation) was used as the phase separation inhibitor C11.

(Phase separation inhibitor C12)
Product name Emarex GWO-360 (polyoxyethylene 60 mol adduct of trioleic acid glyceride, HLB13, manufactured by Nippon Emulsion Co., Ltd.) was designated as phase separation inhibitor C12.

(Phase separation inhibitor C13)
The product name EMALEX GWIS-360 (polyoxyethylene 60 mol adduct of triisostearic acid glyceride, HLB13, manufactured by Nippon Emulsion Co., Ltd.) was designated as phase separation inhibitor C13.

(Phase separation inhibitor TMP)
The product name 1,1,1-tris (hydroxymethyl) propane (trimethylolpropane, manufactured by Wako Pure Chemical Industries, Ltd.) was used as the phase separation inhibitor TMP.
<Purification of castor oil fatty acid>
Purification Example 1 (High purity castor oil fatty acid (1))
A molecular distillation apparatus (manufactured by Shibata Kagaku Co., Ltd.) having a castor oil fatty acid (produced by Ito Oil Co., Ltd .: trade name CO-FA, purity: 86%) obtained by hydrolyzing castor oil and having an evaporation surface area of 0.03 m ² To obtain a high-purity castor oil fatty acid (1).

  The evaporation conditions at this time were a charging speed of 200 g / h, an evaporation surface temperature of 160 ° C., a pressure of 15 Pa, and a wiper rotation speed of 300 rpm.

  The obtained high purity castor oil fatty acid (1) has an acid value of 180.7 mgKOH / g and a hydroxyl value of 172.9 mgKOH / g, and the purity of the high purity castor oil fatty acid (1) determined from these is 95.7. %Met.

  In addition, it was confirmed that the high purity castor oil fatty acid (1) is ricinoleic acid.

<Manufacture of biopolyester polyol>
Synthesis Example 1 (Polyester polyol A-1)
High purity castor oil fatty acid (1) obtained in Purification Example 1 and castor oil fatty acid (manufactured by Ito Oil Co., Ltd .: trade name CO-FA, purity (ricinoleic acid content): 86%) to a purity of 95.0% It mixed so that it might become.

  Next, 1944 g of the obtained mixed castor oil fatty acid, 78 g of SOR-400 (manufactured by Mitsui Chemicals, sorbitol added with propylene oxide, hydroxyl value 400 mg KOH / g), PE-450 (manufactured by Mitsui Chemicals, pentaerythritol) 97 g of a polyol added with propylene oxide and a hydroxyl value of 450 mgKOH / g) are charged into a 2 L glass flask equipped with a thermometer, a stirring device, and a device for separating generated water at 180 ° C. under a nitrogen stream. A condensation reaction was performed. In addition, the average functional group number of the polyhydric alcohol used in this condensation reaction was 4.6.

  Subsequently, when the acid value became 10 mgKOH / g or less, 0.2 g of tetrabutyl orthotitanate (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and subsequently subjected to a condensation reaction at 180 ° C. for 45 hours to obtain polyester polyol A- 1 was obtained.

  The obtained polyester polyol A-1 had a hydroxyl value (OHV) of 51 mgKOH / g, an average functional group number (calculated value) of 4.4, and a viscosity of 4300 mPa · s / 25 ° C. Further, the obtained polyester polyol A-1 was obtained by condensing a plurality of castor oil fatty acids with a polyhydric alcohol.

Synthesis Example 2 (Polyester polyol A-2)
Castor oil fatty acid (made by Ito Oil Co., Ltd .: trade name CO-FA, purity: 86%) 4218 g, SOR-400 (manufactured by Mitsui Chemicals, polyol obtained by adding propylene oxide to sorbitol, hydroxyl value 400 mgKOH / g, average number of functional groups: 6) 547 g was charged into a 2 L glass flask equipped with a thermometer, a stirrer, and a device for separating generated water, and subjected to a condensation reaction in a nitrogen stream at 180 ° C. for 180 hours.

  Next, when the acid value became 10 mgKOH / g or less, 0.5 g of tetrabutyl orthotitanate (reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and subsequently subjected to a condensation reaction at 180 ° C. for 46 hours to obtain polyester polyol A -2 was obtained.

  The obtained polyester polyol A-2 had a hydroxyl value (OHV) of 50 mgKOH / g, an average functional group number (calculated value) of 4.3, and a viscosity of 2700 mPa · s / 25 ° C. Further, the obtained polyester polyol A-2 was obtained by condensing a plurality of castor oil fatty acids with a polyhydric alcohol.

<Manufacture of polyether polyol>
Synthesis Example 3 (Polyether polyol B-1)
Tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide 0.01 mol was added to 1 mol of glycerin and dehydrated under reduced pressure at 100 ° C. for 6 hours.

Next, propylene oxide was added to glycerin at a reaction temperature of 90 ° C. and a maximum reaction pressure of 3.8 kg / cm ² to obtain an intermediate having a hydroxyl value of 28 mgKOH / g, and then ethylene oxide was reacted at a reaction temperature of 100 ° C. at the maximum reaction. Addition polymerization was performed at a pressure of 3.8 kg / cm ² to obtain a polyether polyol B-1.

  The obtained polyether polyol B-1 had a total unsaturation of 0.025 meq / g, a hydroxyl value of 24 mgKOH / g, and a terminal oxyethylene group content of 15% by mass.

Synthesis example 4 (polyether polyol B-2)
0.37 mol of potassium hydroxide was added to 1 mol of glycerin and dehydrated under reduced pressure at 100 ° C. for 6 hours.

Next, propylene oxide was subjected to addition polymerization of glycerin with propylene oxide at a reaction temperature of 115 ° C. and a maximum reaction pressure of 5.0 kg / cm ² to obtain an intermediate having a hydroxyl value of 33 mgKOH / g. by addition polymerization at a pressure 3.8 kg / cm ^2, to obtain a polyether polyol B-2.

  The obtained polyether polyol B-2 had a hydroxyl value of 28 mgKOH / g and a terminal oxyethylene group content of 15% by mass.

Synthesis Example 5 (Polyether polyol B-3)
0.37 mol of potassium hydroxide was added to 1 mol of glycerin and dehydrated under reduced pressure at 100 ° C. for 6 hours.

Subsequently, propylene oxide was added to glycerin at a reaction temperature of 115 ° C. and a maximum reaction pressure of 5.0 kg / cm ² to obtain an intermediate having a hydroxyl value of 65.5 mgKOH / g, and then ethylene oxide was further reacted at a reaction temperature of 100 ° C. Addition polymerization was performed at a maximum reaction pressure of 3.8 kg / cm ² to obtain polyether polyol B-3.

  The obtained polyether polyol B-3 had a hydroxyl value of 56 mgKOH / g and a terminal oxyethylene group content of 14.5% by mass.

Synthesis Example 6 (Polyether polyol B-4)
0.37 mol of potassium hydroxide was added to 1 mol of glycerin and dehydrated under reduced pressure at 100 ° C. for 6 hours.

Subsequently, propylene oxide was added to glycerin at a reaction temperature of 115 ° C. and a maximum reaction pressure of 5.0 kg / cm ² to obtain an intermediate having a hydroxyl value of 40 mgKOH / g, and then ethylene oxide was further reacted at a reaction temperature of 100 ° C. with a maximum reaction. Polyether polyol B-4 was obtained by addition polymerization at a pressure of 3.8 kg / cm ² .

  The obtained polyether polyol B-4 had a hydroxyl value of 34 mgKOH / g and a terminal oxyethylene group content of 15% by mass.

<Production of vinyl monomer modified polyol>
Synthesis Example 7 (Vinyl monomer modified polyol PB-1)
The polyether polyol B-1 (hydroxyl value 24 mgKOH / g) obtained in Synthesis Example 3 is fully filled in a pressure-resistant autoclave equipped with a thermometer, a stirrer, a pressure gauge, and a liquid feeding device. The temperature was raised to 120 ° C. while stirring.

  Subsequently, a mixture of polyether polyol B-1, radical polymerization initiator (2,2′-azobis (2-isobutyronitrile)), acrylonitrile and a dispersion stabilizer was continuously charged, and the reaction temperature was 120 ° C. Acrylonitrile was graft polymerized under conditions of a reaction pressure of 400 kPa and a residence time of 50 minutes, and after removing the initial distillation from the outlet, a reaction solution was continuously obtained.

In addition, the usage-amount of a raw material is as follows.
Polyether polyol B-1: 7200 g (total of the amount charged in the autoclave and the amount used in the mixture)
Radical polymerization initiator: 50 g
Acrylonitrile: 1800 g
Then, the obtained reaction liquid was subjected to a heat and pressure treatment for 3 hours under conditions of 120 ° C. and 655 Pa or less to remove unreacted acrylonitrile, decomposition products of radical polymerization initiator, and the like. Thereby, vinyl monomer modified polyol PB-1 was obtained.

  The vinyl monomer-modified polyol PB-1 has a hydroxyl value of 19 mgKOH / g and a vinyl polymer content of 20% by mass (the total amount of acrylonitrile used is 20% by mass with respect to the total amount of polyether polyol B-1 and acrylonitrile used). Met.

Synthesis Example 8 (Vinyl monomer modified polyol PB-2)
The polyether polyol B-4 (hydroxyl value 34 mgKOH / g) obtained in Synthesis Example 6 is fully filled in a pressure-resistant autoclave equipped with a thermometer, a stirrer, a pressure gauge, and a liquid feeding device. The temperature was raised to 120 ° C. while stirring.

  Subsequently, a mixture of polyether polyol B-4, radical polymerization initiator (2,2′-azobis (2-isobutyronitrile)), acrylonitrile and a dispersion stabilizer was continuously charged, and the reaction temperature was 120 ° C. Acrylonitrile was graft polymerized under conditions of a reaction pressure of 400 kPa and a residence time of 50 minutes, and after removing the initial distillation from the outlet, a reaction solution was continuously obtained.

  In addition, the usage-amount of a raw material is as follows.

Polyether polyol B-4: 7200 g (sum of the amount charged in the autoclave and the amount used in the mixture)
Radical polymerization initiator: 80 g
Acrylonitrile: 3100 g
Thereafter, the obtained reaction solution was heated and reduced under conditions of 120 ° C. and 655 Pa or less for 3 hours to remove unreacted acrylonitrile, decomposition products of radical polymerization initiator, and the like. Thereby, vinyl monomer modified polyol PB-2 was obtained.

  The vinyl monomer-modified polyol PB-2 has a hydroxyl value of 23 mgKOH / g and a vinyl polymer content of 30% by mass (the total amount of acrylonitrile used is 100% by mass of the total amount of polyether polyol B-4 and acrylonitrile used). 30% by mass).

<Preparation of polyol composition>
Examples 1-13 and Comparative Examples 1-6
By mixing each component with the formulation shown in Tables 1 to 3 and mixing with a lab mixer at room temperature, a polyol composition containing various additives suitable for the production of polyurethane foam was obtained. In addition, each polyol component, phase separation inhibitor, and the like were preliminarily heated to 50 ° C. and blended and mixed. The obtained composition was used as a resin premix. Moreover, in order to make visual observation easy, the obtained polyol composition (namely, resin premix) was defoamed.

<Stability evaluation of resin premix>
30 g of the polyol composition was poured into a screw-mouth test tube (“ST-18M” manufactured by Nidec Rika Glass Co., Ltd .: outer diameter 18 mm, wall thickness 1.2 mm, total length 180 mm, capacity 30 mL), capped and sealed, The appearance (separated state) after standing for a predetermined period and the state of the composition were visually confirmed in a room at 23 ° C. and in an oven at 50 ° C. The evaluation criteria are as follows.
◎: Phase separation cannot be confirmed ○: Phase separation can be confirmed very slightly (1% or less of polyester polyol)
Δ: Phase separation slightly observed (about several percent of polyester polyol)
X: State in which 10 to 80% of the polyester polyol is phase-separated XX: State in which the phase is completely separated In addition, when the composition is solidified or extremely thickened, A comment was written.

<Manufacture of polyurethane foam>
Example 14
18 parts by mass of polyester polyol (A-2), 41 parts by mass of polyether polyol (B-1), 41 parts by mass of polymer polyol (PB-1), 2 parts by mass of phase separation inhibitor C2, and a crosslinking agent act Cole KL-210 (Mitsui Chemicals Co., Ltd.) 1 part by mass, foam stabilizer SZ-1966 (Toray Dow Corning Co., Ltd.) 1 part by mass, foaming agent 3.5 parts by mass of water, and catalyst as a catalyst Riser No. 31 (Amine catalyst, manufactured by Kao Corporation) 0.4 parts by mass, Kao Riser No. 12 0.05 parts by mass (amine catalyst, manufactured by Kao Corporation) and Neostan U-100 (dibutyltin dilaurate, manufactured by Nitto Kasei Co., Ltd.) 0.05 parts by mass were mixed to prepare a resin premix.

  Thereafter, the resin premix and the polyisocyanate component (trade name Cosmonate TM-20, product name Cosmonate TM-20, tolylene diisocyanate, and polymethylene polyphenylene polyisocyanate 80:20 (mass by mass) so that the isocyanate index is 100. Ratio) Mixture) 42.65 parts by mass were mixed and immediately poured into a mold having an internal size of 300 mm × 300 mm × 100 mm adjusted to 65 ° C. in advance, and the lid was closed and foamed.

  Then, after allowing the mold to cure for 6 minutes while maintaining the mold at 65 ° C., the flexible polyurethane foam was taken out of the mold.

Examples 15 to 23, Comparative Examples 7 to 10 and Reference Comparative Examples 1 to 6
A resin premix was prepared in the same manner as in Example 14 except that the formulation shown in Tables 4 to 9 was used, and then a flexible polyurethane foam was obtained in the same manner as in Example 14.

  In each of the examples and comparative examples in Tables 6 and 7, in order to evaluate the polyurethane foam with the same degree of hardness, the formulation of the polyol component was appropriately adjusted.

<Stability evaluation of resin premix>
The stability of the resin premix prepared in the production of polyurethane foam was evaluated according to the above-mentioned criteria by the method described above.

<Evaluation of polyurethane foam>
(1) Core density The skin was removed from the polyurethane foam sample, and the core density was measured as a rectangular parallelepiped foam in accordance with the apparent density measurement method described in JIS K-6400 (1997).

(2) Hardness (25% ILD)
The hardness of a polyurethane foam having a thickness of 100 mm was measured in accordance with method A described in JIS K-6400 (1997).

(3) Tensile strength The tensile strength of the polyurethane foam was measured in accordance with the method described in JIS K-6400 (1997).

(4) Elongation rate The elongation rate of the polyurethane foam was measured according to the method described in JIS K-6400 (1997).

(5) Tear strength The tear strength of the polyurethane foam was measured according to the method described in JIS K-6400 (1997).

(6) Core rebound resilience The resilience of the polyurethane foam was measured according to the method described in JIS K-6400 (1997).
(7) Wet heat compression set (wet set (WS))
The wet set was measured by the method described in JIS K-6400.

  Specifically, the core portion of the molded polyurethane foam was cut out to 50 mm × 50 mm × 25 mm and used as a test piece. Next, the test piece was compressed to a thickness of 50%, sandwiched between parallel flat plates, and allowed to stand for 22 hours at 50 ° C. and a relative humidity of 95%. And the test piece was taken out, the thickness after 30-minute progress was measured, and the distortion rate was measured compared with the thickness before a test.

  Tables 4 to 9 show the formulation of each resin premix and each polyurethane foam, and the evaluation results thereof.

The details of the abbreviations in the table are as follows.
<Polyester polyol>
A-1: Polyester polyol obtained in Synthesis Example 1, hydroxyl value 51 mgKOH / g
A-2: Polyester polyol obtained in Synthesis Example 2, hydroxyl value 50 mgKOH / g
<Polyether polyol>
B-1: Polyether polyol obtained in Synthesis Example 3, hydroxyl value 24 mgKOH / g
B-2: Polyether polyol obtained in Synthesis Example 4, hydroxyl value 28 mgKOH / g
B-3: Polyether polyol obtained in Synthesis Example 5, hydroxyl value 56 mgKOH / g
<Vinyl monomer modified polyol>
PB-1: Vinyl monomer-modified polyol obtained in Synthesis Example 7, hydroxyl value 19 mgKOH / g
PB-2: Vinyl monomer-modified polyol obtained in Synthesis Example 8, hydroxyl value 23 mgKOH / g
<Vegetable oil polyol>
Castor oil special A: castor oil, trade name castor oil special A, hydroxyl value 163 mgKOH / g, manufactured by Ito Oil Co., Ltd. <communication agent>
EP-505S: Trade name Actol EP-505S, hydroxyl value 52 mgKOH / g, manufactured by Mitsui Chemicals <crosslinking agent>
KL-210: Trade name Actol KL-210, polyoxyalkylene polyol having a functional group number of 3.75, hydroxyl value 840 mgKOH / g, Mitsui Chemicals Gly: glycerin, hydroxyl value 1830 mgKOH / g
<Foaming agent>
H ₂ O: Water, hydroxyl value 9 mgKOH / g
<Catalyst>
KL-31: amine catalyst, trade name Kao Raiser No. 31, KL-120 manufactured by Kao Corporation: amine catalyst, trade name Kao Raiser No. 120, 1-isobutyl-2-methylimidazole, KL-12 manufactured by Kao Corporation: amine catalyst, trade name Kao Raiser No. 12, U-100 manufactured by Kao Corporation: Organotin compound, trade name Neostan U-100, dibutyltin dilaurate, manufactured by Nitto Kasei Co., Ltd. <foam stabilizer>
SZ-1966: trade name SZ-1966, manufactured by Toray Dow Corning Y-10366: trade name Y-10366, manufactured by Momentive <polyisocyanate>
TM-20: Cosmonate TM-20, 80 parts by mass of a mixture of 2,4-toluylene diisocyanate and 2,6-toluylene diisocyanate in a mass ratio of 80:20, and 20 parts by mass of polymethylene polyphenylene polyisocyanate, Made by Mitsui Chemicals (consideration)
(1) Consideration about a polyol composition In each Example, since the phase-separation inhibitor containing the polyoxyethylene adduct of a hydroxyl-containing fatty acid ester is used, it is long-term in normal temperature and a comparatively high temperature environment. Over the period, the phase separation of the polyol composition was suppressed, and the stability was excellent.

On the other hand, in each comparative example, a phase separation inhibitor containing a polyoxyethylene adduct of a hydroxyl group-containing fatty acid ester is not used. More specifically, a phase separation inhibitor is not used (Comparative Example 1), or an ether surfactant (Comparative Examples 2 and 3) or a fatty acid ester not containing a hydroxyl group as a phase separation inhibitor. Of polyoxyethylene adducts (Comparative Examples 4 to 6). Therefore, phase separation, solidification, thickening and the like of the polyol composition were observed.
(2) Consideration about polyurethane foam In each example, a phase separation inhibitor containing a polyoxyethylene adduct of a hydroxyl group-containing fatty acid ester is used. The phase separation of the resin premix was suppressed throughout, and a polyurethane foam having excellent physical properties (particularly wet heat compression set (WS)) was obtained.

  On the other hand, in each comparative example, since no phase separation inhibitor was used, phase separation of the resin premix was observed, and physical properties of the polyurethane foam were also inferior.

  On the other hand, in Reference Comparative Examples 2-3 and 5-6, a phase separation inhibitor is used, but since it does not contain a polyoxyethylene adduct of a hydroxyl group-containing fatty acid ester, the phase of the resin premix While the separation was suppressed, the wet heat compression set (WS) of the polyurethane foam was inferior to that of Reference Comparative Examples 1 and 4 in which no phase separation inhibitor was used.

Claims (11)

A polyol composition containing a polyol component and a phase separation inhibitor,
The following component (A) and the following component (B) are contained as a polyol component,
Contains the following component (C) as a phase separation inhibitor ,
The component (C) contains a polyoxyethylene adduct of hardened castor oil,
In the polyoxyethylene adduct of the hardened castor oil, the average number of moles of ethylene oxide added is 45 to 120 moles per mole of the hardened castor oil.
A polyol composition characterized by the above.
Component (A): Polyester polyol which is a condensate of a plant-derived fatty acid which may be condensed and a polyhydric alcohol Component (B): Polyether polyol Component (C): Polyoxyethylene addition of a hydroxyl group-containing fatty acid ester object   The polyol composition according to claim 1, wherein the plant-derived fatty acid contains a hydroxyl group-containing fatty acid.   The polyol composition according to claim 1, wherein the plant-derived fatty acid contains castor oil fatty acid.   The polyol composition according to claim 2 or 3, wherein the hydroxyl group-containing fatty acid contains a hydroxyl group-containing monocarboxylic acid.   The polyol composition according to any one of claims 2 to 4, wherein the hydroxyl group-containing fatty acid contains ricinoleic acid. The component (A), the component (B), the polyoxyethylene adduct of a hydroxyl group-containing fatty acid ester (component (CS)) whose average addition mole number of ethylene oxide is pS, and the average addition mole number of ethylene oxide are pL. At least a polyoxyethylene adduct (component (CL)) of a hydroxyl group-containing fatty acid ester is blended,
pS <characterized in that it is a pL, polyol composition according to any one of claims 1-5. The polyol composition according to any one of claims 1 to 6 , wherein the hydroxyl value of the component (B) is 15 mgKOH / g or more and 80 mgKOH / g or less. The polyol composition according to any one of claims 1 to 7 , wherein the hydroxyl value of the component (A) is from 30 mgKOH / g to 120 mgKOH / g. For a total amount of 100 parts by mass of the polyol component and the phase separation inhibitor,
The polyol composition according to any one of claims 1 to 8 , wherein a content ratio of the component (A) is 5 parts by mass or more and 50 parts by mass or less. For a total amount of 100 parts by mass of the polyol component and the phase separation inhibitor,
The polyol composition according to any one of claims 1 to 9 , wherein a content ratio of the component (C) is 0.5 parts by mass or more and 10 parts by mass or less. The polyol composition according to any one of claims 1 to 10 ,
A polyurethane foam obtained by reacting with a polyisocyanate component.